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EP2203511A1 - Polymer material and method for the production thereof - Google Patents

Polymer material and method for the production thereof

Info

Publication number
EP2203511A1
EP2203511A1 EP08841590A EP08841590A EP2203511A1 EP 2203511 A1 EP2203511 A1 EP 2203511A1 EP 08841590 A EP08841590 A EP 08841590A EP 08841590 A EP08841590 A EP 08841590A EP 2203511 A1 EP2203511 A1 EP 2203511A1
Authority
EP
European Patent Office
Prior art keywords
polymeric material
mixture
polyester
weight
starch
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP08841590A
Other languages
German (de)
French (fr)
Other versions
EP2203511B1 (en
Inventor
Harald Schmidt
Christoph Hess
Johannes Mathar
Ralf Hackfort
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BioTec Biologische Naturverpackungen GmbH and Co KG
Original Assignee
BioTec Biologische Naturverpackungen GmbH and Co KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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Application filed by BioTec Biologische Naturverpackungen GmbH and Co KG filed Critical BioTec Biologische Naturverpackungen GmbH and Co KG
Priority to PL08841590T priority Critical patent/PL2203511T3/en
Priority to DK12156095.7T priority patent/DK2497797T4/en
Priority to EP12156095.7A priority patent/EP2497797B2/en
Publication of EP2203511A1 publication Critical patent/EP2203511A1/en
Application granted granted Critical
Publication of EP2203511B1 publication Critical patent/EP2203511B1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L3/00—Compositions of starch, amylose or amylopectin or of their derivatives or degradation products
    • C08L3/02—Starch; Degradation products thereof, e.g. dextrin
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/06—Biodegradable
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
    • C08L23/0869—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen with unsaturated acids, e.g. [meth]acrylic acid; with unsaturated esters, e.g. [meth]acrylic acid esters
    • C08L23/0884—Epoxide-containing esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C08L33/068—Copolymers with monomers not covered by C08L33/06 containing glycidyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Definitions

  • the invention relates to a starch-containing polymeric material, a process for its preparation and molded parts, films and / or fibers produced from the material.
  • Starch-based polymer blends which starch is used in combination with one or more thermoplastic polymers, e.g. As polyesters, are well known.
  • thermoplastic polymers e.g. As polyesters.
  • plasticizer-free starch-containing polymer blends are described, for example, in the publications EP 0 596 437 Bl and EP 0 917 540 B1.
  • plasticizer-free starch-containing polymer blends contain starch up to a maximum amount of about 33% by weight, based on the total composition of the polymer blend.
  • thermoplastic polymer blend A plasticizer-free thermoplastic polymer blend
  • the object of the invention is to improve the mechanical properties of the starch-containing materials mentioned at the outset and of the products produced therefrom (for example molded parts, films and / or fibers).
  • the invention has for its object to provide plasticizer-free polymer blends based on starch, which have the highest possible starch content with excellent mechanical properties.
  • An essential feature of the process according to the invention is the addition of an epoxy group-containing polymer. It has surprisingly been found that the presence of polymers containing epoxide groups as an additive in the preparation of starch-containing polymeric materials leads to a substantial improvement in the mechanical properties of the material, in particular its tensile strength, elongation at break and dart drop values.
  • the polymeric material produced by the process according to the invention is characterized by excellent mechanical properties.
  • a film produced from the polymeric material has a tensile strength according to DIN 53455 of 5 to 60 N / mm 2 , in particular from 10 to 40 N / mm 2 and / or an elongation at break according to DIN 53455 of 100 to 1000%, in particular from 200 to 800%.
  • the process according to the invention also makes it possible to produce for the first time plasticizer-free polymer blends based on starch with a starch content greater than or equal to 34% by weight, films produced from the polymer blends having an elongation at break according to DIN 53455 of at least 300% and / or a dart drop value according to ASTM D-1709 of at least 10 g / ⁇ m.
  • the process according to the invention provides that a mixture comprising starch or starch derivative, polyester and polymer containing epoxide groups is homogenized.
  • the preparation of starch-containing thermoplastic polymers by homogenizing a starch-containing starting mixture is well known and usually takes place in an extruder. Suitable preparation processes for starch-containing thermoplastic polymers are described, for example, in the publications EP 0 596 437 Bl and EP 0 917 540 B1.
  • the starch or starch derivative used in the process according to the invention are preferably selected from native potato starch, tapioca starch, rice starch and corn starch.
  • the mixture contains 5 to 75% by weight, in particular 10 to 75% by weight, preferably 15 to 70% by weight, more preferably 25 to 55% by weight, most preferably 34 to 51% by weight starch and / or starch derivative.
  • the polyester contained in the mixture is preferably selected from the group consisting of aliphatic-aromatic copolyester, aliphatic polyester, aromatic polyester, PHA, PLA, PHB and PHBV.
  • polyester for the method in question which are in accordance with EN 13432 biodegradable and / or a glass transition temperature (Tg) less than 0 ° C, in particular less -4 0 C, more preferably less than -1O 0 C, even more preferably less than -2O 0 C and most preferably less TM o
  • polyesters used in the process according to the invention are furthermore preferably thermoplastic.
  • the polyester used is an aliphatic-aromatic polyester, a copolyester, in particular a random copolyester, based on at least adipic acid. More preferably, it is a copolyester or random copolyester based on 1,4-butanediol, adipic acid and terephthalic acid or terephthalic acid derivative (eg dimethyl terephthalate DMT).
  • This may in particular have a glass transition temperature (Tg) of -25 to -40 0 C, in particular -30 to -35 0 C, and / or a melting range of 100 to 120 0 C, in particular 105 to 115 0 C, have.
  • Tg glass transition temperature
  • polyesters which are selected from the group consisting of polyhydroxvalerate, polyhydroxybutyrate-hydroxyvalerate copolymer and polycaprolactone. More preferred aliphatic polyesters are those based on succinate, wherein the polyester may in particular be selected from the group consisting of polybutylene succinate (PBS), polybutylene succinate adipate (PBSA) and polyethylene succinate (PES) or mixtures thereof.
  • PBS polybutylene succinate
  • PBSA polybutylene succinate adipate
  • PES polyethylene succinate
  • the content of polyester in the mixture is preferably from 20 to 85% by weight, in particular from 30 to 80% by weight, more preferably from 40 to 80% by weight, based on the total composition.
  • the polymeric material according to the invention also contains an epoxy group-containing polymer, which is preferably a copolymer containing epoxide groups. Suitable polymers or copolymers containing epoxide groups are, in particular, those which have a molecular weight (M w ) of from 1,000 to 25,000, in particular from 3,000 to 10,000.
  • the epoxy group-containing polymer is a glycidyl (meth) acrylate-containing polymer.
  • a suitable glycidyl (meth) acrylate-containing polymer is, for example, a copolymer of (a) styrene and / or ethylene and / or methyl methacrylate and / or methyl acrylate and (b) glycidyl (meth) acrylate.
  • glycidyl (meth) acrylate-containing polymer is a copolymer selected from the group consisting of styrene-methyl methacrylate-glycidyl methacrylate, ethylene-methyl acrylate-glycidyl methacrylate and ethylene-glycidyl methacrylate.
  • glycidyl (meth) acrylate is preferably contained in an amount of 1 to 60% by weight, especially 5 to 55% by weight, more preferably 45 to 52% by weight, based on the total composition of the glycidyl (meth) acrylate-containing polymer.
  • epoxy-containing copolymers are also epoxy-containing copolymers based on styrene, ethylene, acrylic acid esters and / or methacrylic acid in question.
  • the mixture preferably contains 0.01 to 5% by weight, in particular 0.05 to 3% by weight, more preferably 0.1 to _ "i _
  • Epoxide group-containing polymer 2 wt.% Epoxide group-containing polymer, based on the total composition.
  • the mixture may contain customary additives such as, for example, processing aids, plasticizers, stabilizers, modifiers and / or fillers.
  • the inventive method provides that the mixture is homogenized. Homogenization can be carried out by any measures known to those skilled in the art of plastics engineering. Preferably, the mixture is homogenized by dispersing, stirring, kneading and / or extruding. According to a preferred embodiment of the invention, shear forces act on the mixture during homogenization. Suitable preparation processes for starch-containing thermoplastic polymers which can also be used analogously for the preparation of the polymeric material according to the invention are described, for example, in the publications EP 0 596 437 B1 and EP 0 917 540 B1.
  • the mixture during homogenization (z. B. in the extruder) is heated, preferably to a temperature of 90 to 250 0 C, in particular 130 to 22O 0 C.
  • the water content of the mixture is preferably less than 10% by weight, in particular less than 7% by weight, more preferably less than 5% by weight, in particular less than 3% by weight, more preferably less than 1.5% by weight, and most preferably less than 1% by weight, based on the total composition.
  • the water content is adjusted by drying during homogenization.
  • the drying process can be carried out, for example, by degassing the mixture or the melt, expediently by removing steam during the extrusion.
  • the polymeric material produced by the process according to the invention has thermoplastic properties.
  • the material is thermoplastically processable.
  • the process according to the invention makes it possible to prepare starch-based plasticizer-free thermoplastic polymer blends which have a starch content of at least 34% by weight and at the same time have excellent mechanical properties.
  • Plasticizer-free in this context means in particular that the polymer blends contain no glycerol and / or sorbitol.
  • From the polymeric material produced by the process according to the invention can be produced in particular films having an elongation at break according to DIN 53455 of at least 200% and / or a dart drop value according to ASTM D-1709 of at least 5 g / micron.
  • the invention therefore further relates to a starch-containing thermoplastically processable polymeric material, wherein (a) the polymeric material contains less than 10% by weight, based on the total composition, of low molecular weight substances,
  • the amount of starch of the polymeric material is at least 34% by weight
  • a film produced from the polymeric material has an elongation at break according to DIN 53455 of at least 200% and / or a dart drop value according to ASTM D-1709 of at least 5 g / ⁇ m.
  • the starch-containing material according to the invention contains less than about 10% by weight of low molecular weight substances and is thus essentially free from plasticizer.
  • Low molecular weight substances in the context of the invention are understood to mean substances having a molecular weight of less than 500 g / mol, in particular less than 250 g / mol.
  • Low molecular weight substances according to the invention are in particular water, glycerol, sorbitol and / or mixtures thereof.
  • the polymeric material according to the invention contains less than 7% by weight, in particular less than 5% by weight, preferably less than 3% by weight, based on the total composition, of low molecular weight substances. According to a further preferred embodiment of the invention, the polymeric material according to the invention contains no glycerol and / or sorbitol.
  • the starch content of the polymeric material is at least 35% by weight, in particular at least 36% by weight, preferably at least 37% by weight, more preferably at least 38 wt. %, and most preferably at least 39% by weight.
  • the polymeric material according to the invention may further contain as further constituent a polyester, preferably in an amount of less than 70% by weight, in particular less than 65% by weight, more preferably less than 60% by weight, most preferably less than 55% by weight.
  • the polymeric materials of the invention are suitable for a variety of purposes.
  • the materials are suitable for the production of moldings, films or fibers.
  • the invention consequently also relates to molded parts, films or fibers produced from the materials according to the invention.
  • aliphatic-aromatic copolyester was a random copolyester based on 1, 4-butanediol, adipic acid and terephthalic acid with a Glass transition temperature (Tg) of -30 to -35 0 C and a melting range of 105 to 115 ° C used.
  • Tg Glass transition temperature
  • epoxy group-containing polymer a random copolymer based on styrene-methyl methacrylate-glycidyl methacrylate having a molecular weight M w of about 6800 and an epoxy group equivalent weight of 285 g / raol was used (additive A).
  • the mixture was intensively mixed in the extruder in a temperature range of 150 to 190 0 C, wherein the melt was simultaneously degassed to remove the mixture of water.
  • the result was a homogeneous melt, which could be withdrawn and granulated.
  • the water content of the homogenized in the manner described, melt processable mass was less than 1 wt.%.
  • a biphasic blend was formed in which the starch forms the disperse and the aliphatic-aromatic copolyester forms the continuous phase.
  • epoxide group-containing polymer i.e., glycidyl-containing polymer
  • glycidyl-containing polymer resulted in an intra- and intermolecular chemical linkage of starch and aliphatic-aromatic copolyester, which had a significant effect on the mechanical properties of the thermoplastic blend produced.
  • Example 1 There were various starchy polymeric materials of aliphatic-aromatic copolyester (59.5 to 66.1 wt.%), Native potato starch (33.4 to 40 wt.%) And epoxid phenomenon inconveniencem copolymer (0.5 wt.%) According to Example 1 produced.
  • the proportion of native potato starch was varied stepwise from 33.4 to 40% by weight at the expense of the aromatic-aliphatic copolyester (see FIGS. 1 and 2).
  • polymeric material without glycidyl additive of aliphatic-aromatic copolyester (66.6 wt.%) And native potato starch (33.4 wt.%) was prepared according to the procedure described in Example 1.
  • blown films were produced from the polymer materials produced and their mechanical properties were determined.
  • ZF tensile strength
  • RD elongation at break
  • MFR MeIt Flow Rate
  • dart drop values puncture resistance
  • Figure 1 shows the tensile strengths and elongation at break of the films produced at different levels of starch.
  • the corresponding glycidyl-modified film with the same starch content (33.4% by weight) has a substantially higher tensile strength. This difference leads to comparable tensile strengths of standard films with 33.4% strength and glycidyl-modified films with 40% strength due to the generally decreasing tensile strength with increasing starch content.
  • the elongation at break value of the glycidyl-modified film does not differ from that of the standard film.
  • films of polyr ⁇ eren material of the same composition without glycidyl additive with more than 34% starch content are extremely granular, brittle and brittle, so that a determination of mechanical characteristics is practically impossible.
  • FIG. 2 shows the MFR (melt flow rate) and the dart drop (puncture resistance) of glycidyl-modified films with increasing starch content. From Figure 2 shows that with increasing starch content both curves fall only slightly. While the dart drop values for the standard formula without glycidyl additive and the modified formula are at the same level, the glycidyl additive causes an MFR reduction to less than half of the standard value.
  • the MFR level of the glycidyl-treated formulations which is significantly reduced in comparison to the standard film without glycidyl additive, can be attributed to the epoxide-induced crosslinking of the polymer chains-without being bound to any particular theory.
  • the MFR therefore appears to be a suitable parameter for assessing the chemical conversion of corresponding chain extenders / crosslinkers.
  • Example 2 was repeated with three different epoxy group-containing polymers (glycidyl additives).
  • starchy polymeric materials have been prepared from aliphatic-aromatic copolyester (59.5 to 66.1 weight percent), native potato starch (33.4 to 40 weight percent), and epoxy group-containing copolymer (additive A, B or C, see below). (0.5 wt.%) Prepared according to the procedure described in Example 1. The proportion of native potato starch was varied stepwise from 33.4 to 40% by weight at the expense of the aromatic-aliphatic copolyester (see FIGS. 3 and 4).
  • polymeric material without glycidyl additive of aliphatic-aromatic copolyester (66.6 wt.%) And native potato starch (33.4 wt.%) was prepared according to the procedure described in Example 1.
  • additive A a random copolymer based on styrene-methyl methacrylate-glycidyl methacrylate having a molecular weight M w of about 6800 and an epoxy group equivalent weight of 285 g / mol was used.
  • additive B a random copolymer based on ethylene-methyl acrylate-glycidyl methacrylate with about 24% by weight of methyl acrylate, 68% by weight of ethylene and 8% by weight of glycidyl methacrylate and an epoxy group equivalent weight of 1775 g / mol was used.
  • additive C a random copolymer based on ethylene-glycidyl methacrylate with about 92% by weight of ethylene and 8% by weight of glycidyl methacrylate and an epoxy group equivalent weight of 1775 g / mol was used.
  • the glycidyl-types used differed in particular in their content of reactive epoxy units.
  • the mass-based concentration of epoxy units in additive A is higher by a factor of 6.23 than in additives 2 and 3. Accordingly, with the same initial weight, additive B resp.
  • Additive C less than one-sixth of reactive epoxide groups compared to Additive A.
  • FIGS. 3 and 4 show, by way of example, the starch content-dependent development of tensile strength and MFR of starch-containing polymeric materials according to Example 2, mixed with in each case 0.5% of the additives A, B or C.
  • FIG. 3 shows that the tensile strength of the films in the case of additive A increases linearly with increasing starch content, whereas it decreases in the case of additives 2 and 3.
  • FIG. 4 shows that the MFR values, which decrease linearly with increasing starch content, are very low for the material treated with additive A.
  • the proportion of native potato starch was varied stepwise from 33.4 to 42% by weight at the expense of the aromatic-aliphatic copolyester (see FIGS. 5 and 6).
  • the proportion of the epoxide group-containing polymer (additive A) was varied at the expense of the aromatic-aliphatic copolyester.
  • polymeric material without glycidyl additive of aliphatic-aromatic copolyester (66.6 wt.%) And native potato starch (33.4 wt.%) was prepared according to the procedure described in Example 1.
  • FIG. 5 shows the profile of the melt flow rate (MFR) of blown films produced from the materials as a function of the starch content and the additive concentration. From the data, it can be seen that the melt flow rate (MFR) (i.e., fluidity) decreases with increasing starch content and increasing glycidyl concentration in the materials. Compared to the standard formula (circle), the MFR value of the formulation with 42% by weight starch and 0.5% by weight glycidyl additive drops to less than one fifth (triangle), a sign of extensive crosslinking of the polymers contained.
  • MFR melt flow rate
  • this course may be followed by a crosslinking reaction of the Glycidyl additive can be explained with the polyester or the starch.
  • the erratic MFR halving at 40% by weight of the solid-to-dashed curve transition shows that the decreasing MFR value is not due solely to an increase in starch content (as in the case of the solid curve, between 33 and 40% by weight) is), but can be significantly attributed to an increased implementation of the concentrated glycidyl additive used.
  • FIG. 6 shows the profile of tensile strength (ZF), elongation at break (RD) and dart drop (DD) for films with different levels of starch and glycidyl additive. While ZF and RD decrease with increasing starch content, the DD value remains at a constant level.
  • the glycidyl additives 1 and 2 of Example 3 were compared at equivalent glycidyl levels.
  • a starchy polymeric material was prepared from aliphatic-aromatic copolyester (59.9 wt.%), Native potato starch (40 wt.%) And additive A from Example 3 (0.1 wt.%) According to the procedure described in Example 1 ,
  • FIG. 7 shows the results:
  • FIG. 7 shows that additives 1 and 2 lead to comparable material properties of the polymeric material with quantitatively equivalent glycidyl fractions (0.1% by weight of additive A versus 0.6% by weight of additive B). Only the value for the elongation at break (RD) is markedly higher in the case of the additive B-containing film.
  • the material properties of generic starch-containing polymeric materials can be significantly changed by adding glycidyl-containing additives. While conventional starchy polymeric materials lack glycidyl additive above about 34 wt. % have insufficient mechanical properties, already allows a content of 0.1% of glycidyl additive, the production of a polymeric material having a starch content of 40 wt. % with simultaneously excellent mechanical properties.
  • the glycidyl additive acts as a compatibilizer between the otherwise incompatible polymers starch and polyester.
  • the efficiency of polymer crosslinking manifests itself in increased tensile strength values while maintaining a low melt flow rate (MFR).

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Graft Or Block Polymers (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Polysaccharides And Polysaccharide Derivatives (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Beans For Foods Or Fodder (AREA)
  • Wrappers (AREA)
  • Artificial Filaments (AREA)

Abstract

Preparing starch-containing polymeric materials comprises: (a) preparing a mixture comprising at least one of 1-75 wt.% of starch and/or its derivative, 10-85 wt.% of polyester and 0.01-7 wt.% of an epoxide group containing polymer; (b) homogenizing the mixture under the provision of thermal and/or mechanical energy; (c) adjusting the water content of the mixture so that the end product contains a water content of less than 12 wt.%, relative to the total composition of the mixture. Independent claims are included for: (1) the polymeric material prepared by the method; and (2) a starch-containing thermoplastic processible polymeric material comprising less than 10 wt.%, relative to the total composition of the polymeric material containing low molecular substances, at least 34 wt.% of the starch portion and foil prepared from the polymeric material having an ultimate elongation of at least 200%, according to DIN 53455 and/or a Dart-drop value of at least 5 g/mu m, according to ASTM D-1709.

Description

Polymeres Material und Verfahren zu dessen Herstellung Polymeric material and process for its preparation

Die Erfindung betrifft ein stärkehaltiges polymeres Material, ein Verfahren zu dessen Herstellung sowie aus dem Material hergestellte Formteile, Folien und/oder Fasern .The invention relates to a starch-containing polymeric material, a process for its preparation and molded parts, films and / or fibers produced from the material.

Polymer-Blends auf Stärkebasis, welche Stärke in Kombination mit einem oder mehreren thermoplastischen Polymeren, z. B. Polyestern, enthalten, sind allgemein bekannt. Die Herstellung und Eigenschaften von weichmacherfreien stärkehaltigen Polymer-Blends werden beispielsweise in den Druckschriften EP 0 596 437 Bl und EP 0 917 540 Bl beschrieben.Starch-based polymer blends which starch is used in combination with one or more thermoplastic polymers, e.g. As polyesters, are well known. The preparation and properties of plasticizer-free starch-containing polymer blends are described, for example, in the publications EP 0 596 437 Bl and EP 0 917 540 B1.

In der Regel enthalten weichmacherfreie stärkehaltige Polymer-Blends Stärke bis zu einem Mengenanteil von maximal etwa 33 Gew.%, bezogen auf die Gesamtzusammensetzung des Polymer-Blends. Obwohl eine weitere Erhöhung des Stärkeanteils aus wirtschaftlichen und ökologischen Gründen wünschenswert wäre, ist dies nicht ohne weiteres möglich, da eine Erhöhung des Stärkeanteils in der Regel mit einer erheblichen Verschlechterung der mechanischen Eigenschaften des Polymers einhergeht.As a rule, plasticizer-free starch-containing polymer blends contain starch up to a maximum amount of about 33% by weight, based on the total composition of the polymer blend. Although a further increase in the starch content would be desirable for economic and ecological reasons, this is not readily possible, since an increase in the starch content is usually accompanied by a significant deterioration in the mechanical properties of the polymer.

Ein weichmacherfreies thermoplastisches Polymer-Blend aufA plasticizer-free thermoplastic polymer blend

Stärkebasis, das sich insbesondere zurStarch, especially for

Blasfolienextrusion, Flachfolienextrusion und zum Spritzgießen von vollständig biologisch abbaubaren Produkten eignet, ist unter dem Handelsnamen "Bioplast® GF 106/02" von der Firma Biotec GmbH & Co. KG in Emmerich (Deutschland) kommerziell erhältlich.Blown film extrusion, flat film extrusion and Injection molding of completely biodegradable products is, by the firm Biotec GmbH Co. KG in Emmerich (Germany) is commercially available under the trade name "Bioplast ® GF 106/02".

Der Erfindung liegt die Aufgabe zugrunde, die mechanischen Eigenschaften der eingangs genannten stärkehaltigen Materialien sowie der daraus hergestellten Produkte (z. B. Formteile, Folien und/oder Fasern) zu verbessern. Insbesondere liegt der Erfindung die Aufgabe zugrunde, weichmacherfreie Polymer-Blends auf Stärkebasis bereitzustellen, die einen möglichst hohen Stärkegehalt bei gleichzeitig ausgezeichneten mechanischen Eigenschaften aufweisen.The object of the invention is to improve the mechanical properties of the starch-containing materials mentioned at the outset and of the products produced therefrom (for example molded parts, films and / or fibers). In particular, the invention has for its object to provide plasticizer-free polymer blends based on starch, which have the highest possible starch content with excellent mechanical properties.

Diese Aufgabe wird erfindungsgemäß durch ein Verfahren zur Herstellung eines polymeren Materials gelöst, welches gekennzeichnet ist durch:This object is achieved by a method for producing a polymeric material, which is characterized by:

(a) Herstellen eines Gemischs enthaltend wenigstens(a) preparing a mixture containing at least

- 1 bis 75 Gew.% Stärke und/oder Stärkederivat,From 1 to 75% by weight of starch and / or starch derivative,

- 10 bis 85 Gew.% Polyester und10 to 85% by weight of polyester and

- 0,01 bis 7 Gew.% eines epoxidgruppenhaltigen Polymers;0.01 to 7% by weight of an epoxy group-containing polymer;

(b) Homogenisieren des Gemischs unter Zuführen von thermischer und/oder mechanischer Energie;(b) homogenizing the mixture by applying thermal and / or mechanical energy;

(c) Einstellen des Wassergehalts des Gemischs, so dass das Endprodukt einen Wassergehalt von kleiner etwa 12 Gew.%, bezogen auf die Gesamtzusammensetzung des Gemischs, aufweist. Vorteilhafte Ausgestaltungen der Erfindung sind in den Unteransprüchen beschrieben.(c) adjusting the water content of the mixture so that the final product has a water content of less than about 12% by weight, based on the total composition of the mixture. Advantageous embodiments of the invention are described in the subclaims.

Ein wesentliches Merkmal des erfindungsgemäßen Verfahrens ist die Zugabe eines epoxidgruppenhaltigen Polymers. Überraschend wurde festgestellt, dass die Gegenwart von epoxidgruppenhaltigen Polymeren als Additiv bei der Herstellung von stärkehaltigen polymeren Materialien zu einer wesentlichen Verbesserung der mechanischen Eigenschaften des Materials, insbesondere dessen Zugfestigkeit , Reißdehnung und Dart-Drop-Werten, führt.An essential feature of the process according to the invention is the addition of an epoxy group-containing polymer. It has surprisingly been found that the presence of polymers containing epoxide groups as an additive in the preparation of starch-containing polymeric materials leads to a substantial improvement in the mechanical properties of the material, in particular its tensile strength, elongation at break and dart drop values.

Das nach dem erfindungsgemäßen Verfahren hergestellte polymere Material zeichnet sich durch ausgezeichnete mechanische Eigenschaften aus. So kann eine aus dem polymeren Material hergestellte Folie eine Zugfestigkeit gemäß DIN 53455 von 5 bis 60 N/mm2, insbesondere von 10 bis 40 N/mm2 und/oder eine Reißdehnung gemäß DIN 53455 von 100 bis 1000 %, insbesondere von 200 bis 800 %, aufweisen .The polymeric material produced by the process according to the invention is characterized by excellent mechanical properties. Thus, a film produced from the polymeric material has a tensile strength according to DIN 53455 of 5 to 60 N / mm 2 , in particular from 10 to 40 N / mm 2 and / or an elongation at break according to DIN 53455 of 100 to 1000%, in particular from 200 to 800%.

Mit dem erfindungsgemäßen Verfahren sind ferner erstmals weichmacherfreie Polymer-Blends auf Stärkebasis mit einen Stärkegehalt größer gleich 34 Gew.% herstellbar, wobei aus den Polymer-Blends hergestellte Folien eine Reißdehnung gemäß DIN 53455 von mindestens 300 % und/oder einen Dart-Drop-Wert gemäß ASTM D-1709 von mindestens 10 g/μm aufweisen.The process according to the invention also makes it possible to produce for the first time plasticizer-free polymer blends based on starch with a starch content greater than or equal to 34% by weight, films produced from the polymer blends having an elongation at break according to DIN 53455 of at least 300% and / or a dart drop value according to ASTM D-1709 of at least 10 g / μm.

Das erfindungsgemäße Verfahren sieht vor, dass ein Gemisch enthaltend Stärke bzw. Stärkederivat, Polyester und epoxidgruppenhaltiges Polymer homogenisiert wird. Die Herstellung von stärkehaltigen thermoplastischen Polymeren durch Homogenisieren eines stärkehaltigen Ausgangsgemischs ist allgemein bekannt und erfolgt üblicherweise in einem Extruder. Geeignete Herstellungsverfahren für stärkehaltige thermoplastische Polymere sind beispielsweise in den Druckschriften EP 0 596 437 Bl und EP 0 917 540 Bl beschrieben.The process according to the invention provides that a mixture comprising starch or starch derivative, polyester and polymer containing epoxide groups is homogenized. The preparation of starch-containing thermoplastic polymers by homogenizing a starch-containing starting mixture is well known and usually takes place in an extruder. Suitable preparation processes for starch-containing thermoplastic polymers are described, for example, in the publications EP 0 596 437 Bl and EP 0 917 540 B1.

Die im erfindungsgemäßen Verfahren eingesetzte Stärke bzw. das Stärkederivat sind vorzugsweise ausgewählt aus nativer Kartoffelstärke, Tapiokastärke, Reisstärke und Maisstärke .The starch or starch derivative used in the process according to the invention are preferably selected from native potato starch, tapioca starch, rice starch and corn starch.

Gemäß einer bevorzugten Ausführungsform der Erfindung enthält das Gemisch 5 bis 75 Gew.%, insbesondere 10 bis 75 Gew.%, vorzugsweise 15 bis 70 Gew.%, noch bevorzugter 25 bis 55 Gew.%, am bevorzugtesten 34 bis 51 Gew.% Stärke und/oder Stärkederivat.According to a preferred embodiment of the invention, the mixture contains 5 to 75% by weight, in particular 10 to 75% by weight, preferably 15 to 70% by weight, more preferably 25 to 55% by weight, most preferably 34 to 51% by weight starch and / or starch derivative.

Der im Gemisch enthaltene Polyester ist vorzugsweise ausgewählt aus der Gruppe bestehend aus aliphatisch- aromatischem Copolyester, aliphatischem Polyester, aromatischen Polyester, PHA, PLA, PHB und PHBV.The polyester contained in the mixture is preferably selected from the group consisting of aliphatic-aromatic copolyester, aliphatic polyester, aromatic polyester, PHA, PLA, PHB and PHBV.

Für das erfindungsgemäße Verfahren kommen insbesondere (aber nicht ausschließlich) Polyester in Frage, die gemäß EN 13432 biologisch abbaubar sind und/oder eine Glasübergangstemperatur (Tg) kleiner O0C, insbesondere kleiner -40C, weiter bevorzugt kleiner -1O0C, noch weiter bevorzugt kleiner -2O0C und am bevorzugtesten kleiner ™ oIn particular (but not exclusively) are polyester for the method in question, which are in accordance with EN 13432 biodegradable and / or a glass transition temperature (Tg) less than 0 ° C, in particular less -4 0 C, more preferably less than -1O 0 C, even more preferably less than -2O 0 C and most preferably less ™ o

-3O0C aufweisen. Die im erfindungsgemäßen Verfahren eingesetzten Polyester sind ferner vorzugsweise thermoplastisch .-3O 0 C have. The polyesters used in the process according to the invention are furthermore preferably thermoplastic.

Gemäß einer besonders bevorzugten Ausführungsform der Erfindung wird als Polyester ein aliphatisch-aromatischer Polyester ein Copolyester, insbesondere ein statistischer Copolyester, auf Basis von mindestens Adipinsäure eingesetzt. Weiter bevorzugt handelt es sich um einen Copolyester bzw. statistischen Copolyester auf Basis von 1, 4-Butandiol, Adipinsäure und Terephthalsäure bzw. Terephthalsäurederivat (z. B. Dimethylterephthalat DMT) . Dieser kann insbesondere eine Glasübergangstemperatur (Tg) von -25 bis -40 0C, insbesondere -30 bis -35 0C, und/oder einen Schmelzbereich von 100 bis 120 0C, insbesondere 105 bis 115 0C, aufweisen.According to a particularly preferred embodiment of the invention, the polyester used is an aliphatic-aromatic polyester, a copolyester, in particular a random copolyester, based on at least adipic acid. More preferably, it is a copolyester or random copolyester based on 1,4-butanediol, adipic acid and terephthalic acid or terephthalic acid derivative (eg dimethyl terephthalate DMT). This may in particular have a glass transition temperature (Tg) of -25 to -40 0 C, in particular -30 to -35 0 C, and / or a melting range of 100 to 120 0 C, in particular 105 to 115 0 C, have.

Geeignete Polyester sind ferner insbesondere aliphatische Polyester, die ausgewählt sind aus der Gruppe bestehend aus Polyhydroxvalerat , Polyhydroxybutyrat-Hydroxyvalerat- Copolymer und Polycaprolacton . Weiter bevorzugte aliphatische Polyester sind solche auf Succinat-Basis, wobei der Polyester insbesondere ausgewählt sein kann aus der Gruppe bestehend aus Polybutylensuccinat (PBS), Polybutylensuccinatadipat (PBSA) und Polyethylensuccinat (PES) oder Mischungen daraus.Further suitable polyesters are in particular aliphatic polyesters which are selected from the group consisting of polyhydroxvalerate, polyhydroxybutyrate-hydroxyvalerate copolymer and polycaprolactone. More preferred aliphatic polyesters are those based on succinate, wherein the polyester may in particular be selected from the group consisting of polybutylene succinate (PBS), polybutylene succinate adipate (PBSA) and polyethylene succinate (PES) or mixtures thereof.

Der Gehalt an Polyester im Gemisch beträgt vorzugsweise 20 bis 85 Gew.%, insbesondere 30 bis 80 Gew.%, noch bevorzugter 40 bis 80 Gew.%, bezogen auf die Gesamtzusammensetzung . Das erfindungsgemäße polymere Material enthält ferner ein epoxidgruppenhaltiges Polymer, wobei es sich vorzugsweise um ein epoxidgruppenhaltiges Copolymer handelt. Als epoxidgruppenhaltige Polymere bzw. Copolymere kommen insbesondere solche in Frage, die ein Molekulargewicht (Mw) von 1.000 bis 25.000, insbesondere 3.000 bis 10.000, aufweisen .The content of polyester in the mixture is preferably from 20 to 85% by weight, in particular from 30 to 80% by weight, more preferably from 40 to 80% by weight, based on the total composition. The polymeric material according to the invention also contains an epoxy group-containing polymer, which is preferably a copolymer containing epoxide groups. Suitable polymers or copolymers containing epoxide groups are, in particular, those which have a molecular weight (M w ) of from 1,000 to 25,000, in particular from 3,000 to 10,000.

Vorzugsweise handelt es sich bei dem epoxidgruppen- haltigen Polymer um ein glycidyl (meth) acrylathaltiges Polymer. Ein geeignetes glycidyl (meth) acrylathaltige Polymer ist beispielsweise ein Copolymer aus (a) Styrol und/oder Ethylen und/oder Methylmethacrylat und/oder Methylacrylat und (b) Glycidyl (meth) acrylat . Besonders gut geeignet als glycidyl (meth) acrylathaltiges Polymer ist ein Copolymer, das ausgewählt ist aus der Gruppe bestehend aus Styrol-Methylmethacrylat- Glycidylmethacrylat , Ethylen-Methylacrylat- Glycidylmethacrylat und Ethylen-Glycidylmethacrylat . Darin ist Glycidyl (meth) acrylat bevorzugt in einer Menge von 1 bis 60 Gew.%, insbesondere 5 bis 55 Gew.%, weiter bevorzugt 45 bis 52 Gew.%, bezogen auf die Gesamtzusammensetzung des glycidyl (meth) acrylathaltigen Polymers, enthalten.Preferably, the epoxy group-containing polymer is a glycidyl (meth) acrylate-containing polymer. A suitable glycidyl (meth) acrylate-containing polymer is, for example, a copolymer of (a) styrene and / or ethylene and / or methyl methacrylate and / or methyl acrylate and (b) glycidyl (meth) acrylate. Particularly suitable as the glycidyl (meth) acrylate-containing polymer is a copolymer selected from the group consisting of styrene-methyl methacrylate-glycidyl methacrylate, ethylene-methyl acrylate-glycidyl methacrylate and ethylene-glycidyl methacrylate. Therein, glycidyl (meth) acrylate is preferably contained in an amount of 1 to 60% by weight, especially 5 to 55% by weight, more preferably 45 to 52% by weight, based on the total composition of the glycidyl (meth) acrylate-containing polymer.

Als epoxidgruppenhaltige Polymere kommen ferner epoxidgruppenhaltige Copolymere auf Basis von Styrol, Ethylen, Acrylsäureester und/oder Methacrylsäureester in Frage .As epoxide-containing polymers are also epoxy-containing copolymers based on styrene, ethylene, acrylic acid esters and / or methacrylic acid in question.

Das Gemisch enthält vorzugsweise 0,01 bis 5 Gew.%, insbesondere 0,05 bis 3 Gew.%, noch bevorzugter 0,1 bis _ "i _The mixture preferably contains 0.01 to 5% by weight, in particular 0.05 to 3% by weight, more preferably 0.1 to _ "i _

2 Gew.% epoxidgruppenhaltiges Polymer, bezogen auf die GesamtZusammensetzung .2 wt.% Epoxide group-containing polymer, based on the total composition.

Das Gemisch kann neben den Hauptbestandteilen Stärke bzw. Stärkederivat, Polyester und epoxidgruppenhaltigem Polymer noch übliche Additive wie zum Beispiel Verarbeitungshilfsmittel, Weichmacher, Stabilisatoren, Äntiflammmittel und/oder Füllstoffe enthalten.In addition to the main constituents starch or starch derivative, polyester and polymer containing epoxide groups, the mixture may contain customary additives such as, for example, processing aids, plasticizers, stabilizers, modifiers and / or fillers.

Das erfindungsgemäße Verfahren sieht vor, dass das Gemisch homogenisiert wird. Das Homogenisieren kann durch beliebige, dem auf dem Gebiet der Kunststofftechnik tätigen Fachmann geläufige Maßnahmen erfolgen. Vorzugweise erfolgt das Homogenisieren des Gemischs durch Dispergieren, Rühren, Kneten und/oder Extrudieren. Gemäß einer bevorzugten Ausführungsform der Erfindung wirken bei der Homogenisierung Scherkräfte auf das Gemisch ein. Geeignete Herstellungsverfahren für stärkehaltige thermoplastische Polymere, die auch auf die Herstellung des erfindungsgemäßen polymeren Materials analog anwendbar sind, sind beispielsweise in den Druckschriften EP 0 596 437 Bl und EP 0 917 540 Bl beschrieben.The inventive method provides that the mixture is homogenized. Homogenization can be carried out by any measures known to those skilled in the art of plastics engineering. Preferably, the mixture is homogenized by dispersing, stirring, kneading and / or extruding. According to a preferred embodiment of the invention, shear forces act on the mixture during homogenization. Suitable preparation processes for starch-containing thermoplastic polymers which can also be used analogously for the preparation of the polymeric material according to the invention are described, for example, in the publications EP 0 596 437 B1 and EP 0 917 540 B1.

Gemäß einer bevorzugten Ausführungsform der Erfindung wird das Gemisch während des Homogenisierens (z. B. im Extruder) erwärmt, vorzugsweise auf eine Temperatur von 90 bis 2500C, insbesondere 130 bis 22O0C.According to a preferred embodiment of the invention the mixture during homogenization (z. B. in the extruder) is heated, preferably to a temperature of 90 to 250 0 C, in particular 130 to 22O 0 C.

Erfindungsgemäß ist es bevorzugt, den Wassergehalt des Gemischs möglichst gering zu halten. Vorzugsweise wird der Wassergehalt des Gemischs auf kleiner 10 Gew.%, insbesondere kleiner 7 Gew.%, weiter bevorzugt kleiner 5 Gew.%, insbesondere kleiner 3 Gew.%, noch bevorzugter kleiner 1,5 Gew.% und am bevorzugtesten kleiner 1 Gew.%, bezogen auf die Gesamtzusammensetzung, eingestellt.According to the invention, it is preferable to keep the water content of the mixture as low as possible. The water content of the mixture is preferably less than 10% by weight, in particular less than 7% by weight, more preferably less than 5% by weight, in particular less than 3% by weight, more preferably less than 1.5% by weight, and most preferably less than 1% by weight, based on the total composition.

Vorzugsweise erfolgt die Einstellung des Wassergehalts durch Trocknen während des Homogenisierens. Der Trocknungsvorgang kann beispielsweise durch Entgasen des Gemischs bzw. der Schmelze, zweckmäßigerweise durch Abziehen von Wasserdampf während des Extrudierens, erfolgen .Preferably, the water content is adjusted by drying during homogenization. The drying process can be carried out, for example, by degassing the mixture or the melt, expediently by removing steam during the extrusion.

Gemäß einer weiteren bevorzugten Ausführungsform der Erfindung besitzt das nach dem erfindungsgemäßen Verfahren hergestellte polymere Material thermoplastische Eigenschaften. Vorzugsweise ist das Material thermoplastisch verarbeitbar.According to a further preferred embodiment of the invention, the polymeric material produced by the process according to the invention has thermoplastic properties. Preferably, the material is thermoplastically processable.

Mit dem erfindungsgemäßen Verfahren ist es möglich, weichmacherfreie thermoplastische Polymer-Blends auf Stärkebasis herzustellen, die einen Stärkegehalt von mindestens 34 Gew.% aufweisen und gleichzeitig ausgezeichnete mechanische Eigenschaften besitzen. Weichmacherfrei bedeutet in diesem Zusammenhang insbesondere, dass die Polymer-Blends kein Glycerin und/oder Sorbitol enthalten. Aus dem nach dem erfindungsgemäßen Verfahren hergestellten polymeren Material lassen sich insbesondere Folien herstellen, die eine Reißdehnung gemäß DIN 53455 von mindestens 200 % und/oder einen Dart-Drop-Wert gemäß ASTM D-1709 von mindestens 5 g/μm aufweisen.The process according to the invention makes it possible to prepare starch-based plasticizer-free thermoplastic polymer blends which have a starch content of at least 34% by weight and at the same time have excellent mechanical properties. Plasticizer-free in this context means in particular that the polymer blends contain no glycerol and / or sorbitol. From the polymeric material produced by the process according to the invention can be produced in particular films having an elongation at break according to DIN 53455 of at least 200% and / or a dart drop value according to ASTM D-1709 of at least 5 g / micron.

Die Erfindung betrifft daher ferner ein stärkehaltiges thermoplastisch verarbeitbares polymeres Material, wobei (a) das polymere Material weniger als 10 Gew.%, bezogen auf die Gesamtzusammensetzung, niedermolekulare Substanzen enthält,The invention therefore further relates to a starch-containing thermoplastically processable polymeric material, wherein (a) the polymeric material contains less than 10% by weight, based on the total composition, of low molecular weight substances,

(b) der Stärkeanteil des polymeren Materials mindestens 34 Gew.% beträgt und(b) the amount of starch of the polymeric material is at least 34% by weight, and

(c) eine aus dem polymeren Material hergestellte Folie eine Reißdehnung gemäß DIN 53455 von mindestens 200 % und/oder einen Dart-Drop-Wert gemäß ASTM D-1709 von mindestens 5 g/μm aufweist.(c) a film produced from the polymeric material has an elongation at break according to DIN 53455 of at least 200% and / or a dart drop value according to ASTM D-1709 of at least 5 g / μm.

Das erfindungsgemäße stärkehaltige Material enthält weniger als etwa 10 Gew.% niedermolekulare Substanzen und ist dadurch im wesentlichen weichmacherfrei. Unter niedermolekularen Substanzen im Sinne der Erfindung werden Substanzen mit einem Molekulargewicht kleiner 500 g/mol, insbesondere kleiner 250 g/mol, verstanden. Niedermolekulare Substanzen im Sinne der Erfindung sind insbesondere Wasser, Glycerin, Sorbitol und/oder Mischungen daraus umfassen.The starch-containing material according to the invention contains less than about 10% by weight of low molecular weight substances and is thus essentially free from plasticizer. Low molecular weight substances in the context of the invention are understood to mean substances having a molecular weight of less than 500 g / mol, in particular less than 250 g / mol. Low molecular weight substances according to the invention are in particular water, glycerol, sorbitol and / or mixtures thereof.

Gemäß einer bevorzugten Äusführungsform der Erfindung enthält das erfindungsgemäße polymere Material weniger als 7 Gew.%, insbesondere weniger als 5 Gew.%, vorzugsweise weniger als 3 Gew.%, bezogen auf die Gesamtzusammensetzung, niedermolekulare Substanzen. Gemäß einer weiteren bevorzugten Ausführungsform der Erfindung enthält das erfindungsgemäße polymere Material kein Glycerin und/oder Sorbitol.According to a preferred embodiment of the invention, the polymeric material according to the invention contains less than 7% by weight, in particular less than 5% by weight, preferably less than 3% by weight, based on the total composition, of low molecular weight substances. According to a further preferred embodiment of the invention, the polymeric material according to the invention contains no glycerol and / or sorbitol.

Gemäß einer weiteren bevorzugten Ausführungsform der Erfindung beträgt der Stärkeanteil des polymeren Materials mindestens 35 Gew.%, insbesondere mindestens 36 Gew.%, vorzugsweise mindestens 37 Gew.%, weiter bevorzugt mindestens 38 Gew . % und am bevorzugtesten mindestens 39 Gew.%.According to a further preferred embodiment of the invention, the starch content of the polymeric material is at least 35% by weight, in particular at least 36% by weight, preferably at least 37% by weight, more preferably at least 38 wt. %, and most preferably at least 39% by weight.

Das erfindungsgemäße polymere Material kann als weiteren Bestandteil ferner einen Polyester, vorzugsweise in einer Menge kleiner 70 Gew.%, insbesondere kleiner 65 Gew,%, noch bevorzugter kleiner 60 Gew.%, am bevorzugtesten kleiner 55 Gew.%, enthalten.The polymeric material according to the invention may further contain as further constituent a polyester, preferably in an amount of less than 70% by weight, in particular less than 65% by weight, more preferably less than 60% by weight, most preferably less than 55% by weight.

Die erfindungsgemäßen polymeren Materialien eignen sich für die verschiedensten Zwecke. Insbesondere eignen sich die Materialien zur Herstellung von Formteilen, Folien oder Fasern. Die Erfindung betrifft folglich auch aus den erfindungsgemäßen Materialien hergestellte Formteile, Folien oder Fasern.The polymeric materials of the invention are suitable for a variety of purposes. In particular, the materials are suitable for the production of moldings, films or fibers. The invention consequently also relates to molded parts, films or fibers produced from the materials according to the invention.

Nachfolgend wird die Erfindung anhand von Ausführungsbeispielen näher beschrieben.The invention will be described in more detail below with reference to exemplary embodiments.

Beispiel 1example 1

Herstellung von glycidyl-modifiziertem stärkehaltigem polymeren MaterialPreparation of glycidyl-modified starchy polymeric material

Ein Gemisch aus nativer Kartoffelstärke, aliphatisch- aromatischem Copolyester und epoxidgruppenhaltigem Polymer in den unten angegebenen Mengenverhältnissen wurde in einen Zweiwellenextruder eingefülltA mixture of native potato starch, aliphatic-aromatic copolyester and epoxy group-containing polymer in the proportions given below was charged into a twin-screw extruder

Als aliphatisch-aromatischer Copolyester wurde ein statistischer Copolyester auf Basis von 1, 4-Butandiol, Adipinsäure und Terephthalsäure mit einer Glasübergangstemperatur (Tg) von -30 bis -350C und einem Schmelzbereich von 105 bis 115°C eingesetzt.As aliphatic-aromatic copolyester was a random copolyester based on 1, 4-butanediol, adipic acid and terephthalic acid with a Glass transition temperature (Tg) of -30 to -35 0 C and a melting range of 105 to 115 ° C used.

Als epoxidgruppenhaltiges Polymer (Glycidyl-Additiv) wurde ein statistisches Copolymer auf Basis von Styrol- Methylmethacrylat-Glycidylmethacrylat mit einem Molekulargewicht Mw von etwa 6800 und einem Epoxygruppenäquivalentgewicht von 285 g/raol eingesetzt (Additiv A) .As the epoxy group-containing polymer (glycidyl additive), a random copolymer based on styrene-methyl methacrylate-glycidyl methacrylate having a molecular weight M w of about 6800 and an epoxy group equivalent weight of 285 g / raol was used (additive A).

Das Gemisch wurde im Extruder in einem Temperaturbereich von 150 bis 1900C intensiv gemischt, wobei die Schmelze gleichzeitig entgast wurde um dem Gemisch Wasser zu entziehen. Es entstand eine homogene Schmelze, die abgezogen und granuliert werden konnte. Der Wassergehalt der in der beschriebenen Weise homogenisierten, thermoplastisch verarbeitbaren Masse lag unter 1 Gew.%.The mixture was intensively mixed in the extruder in a temperature range of 150 to 190 0 C, wherein the melt was simultaneously degassed to remove the mixture of water. The result was a homogeneous melt, which could be withdrawn and granulated. The water content of the homogenized in the manner described, melt processable mass was less than 1 wt.%.

Durch das Mischen und Homogenisieren der Stärke mit aliphatisch-aromatischem Copolyester entstand ein zweiphasiger Blend, in dem die Stärke die disperse und der aliphatisch-aromatische Copolyester die kontinuierliche Phase ausbildet. Die Beimengung von epoxidgruppenhaltigem Polymer (d. h. glycidylhaltigem Polymer) bewirkte eine intra- und intermolekulare chemische Verknüpfung von Stärke und aliphatisch- aromatischem Copolyester, welche sich signifikant auf die mechanischen Eigenschaften des hergestellten thermoplastischen Blends auswirkte.By mixing and homogenizing the starch with aliphatic-aromatic copolyester, a biphasic blend was formed in which the starch forms the disperse and the aliphatic-aromatic copolyester forms the continuous phase. The addition of epoxide group-containing polymer (i.e., glycidyl-containing polymer) resulted in an intra- and intermolecular chemical linkage of starch and aliphatic-aromatic copolyester, which had a significant effect on the mechanical properties of the thermoplastic blend produced.

Aus den hergestellten Materialien wurden Folien mit einer Dicke von ca. 40 μm durch Blasfolienextrusion hergestellt. Hierzu wurde das Granulat in einen Einwellenextruder (L/D = 30, Einzug gekühlt, Sieb 250 μm) gegeben, bei 165 bis 19O0C aufgeschmolzen, über eine Ringdüse (Mono, Düsenspalt 0,8 mm) zum Folienschlauch aufgeblasen (Aufblasverhältnis 3,5) und nach Flachlegung abgezogen .From the produced materials films with a thickness of about 40 microns were produced by blown film extrusion. For this purpose, the granules in a Single-screw extruder (L / D = 30, collection cooled, sieve 250 microns), melted at 165 to 19O 0 C, inflated via an annular nozzle (mono, die gap 0.8 mm) to the film tube (3.5 blow ratio) and deducted after flattening ,

Beispiel 2Example 2

In diesem Beispiel wurde der Einfluss von Glycidyl- Additiv auf die mechanischen Eigenschaften von Blasfolien mit unterschiedlichem Stärkegehalt ermittelt.In this example, the influence of glycidyl additive on the mechanical properties of blown films with different starch content was determined.

Es wurden verschiedene stärkehaltige polymere Materialien aus aliphatisch-aromatischem Copolyester (59,5 bis 66,1 Gew.%), nativer Kartoffelstärke (33,4 bis 40 Gew.%) und epoxidgruppenhaltigem Copolymer (0,5 Gew.%) gemäß Beispiel 1 hergestellt. Der Mengenanteil der nativen Kartoffelstärke wurde dabei auf Kosten des aromatisch- aliphatischen Copolyesters zwischen 33,4 bis 40 Gew.% schrittweise variiert (siehe Figuren 1 und 2) .There were various starchy polymeric materials of aliphatic-aromatic copolyester (59.5 to 66.1 wt.%), Native potato starch (33.4 to 40 wt.%) And epoxidgruppenhaltigem copolymer (0.5 wt.%) According to Example 1 produced. The proportion of native potato starch was varied stepwise from 33.4 to 40% by weight at the expense of the aromatic-aliphatic copolyester (see FIGS. 1 and 2).

Als Vergleichsrezeptur wurde polymeres Material ohne Glycidyl-Additiv aus aliphatisch-aromatischem Copolyester (66,6 Gew.%) und nativer Kartoffelstärke (33,4 Gew.%) gemäß der in Beispiel 1 beschriebenen Vorgehensweise hergestellt .As a comparative formulation, polymeric material without glycidyl additive of aliphatic-aromatic copolyester (66.6 wt.%) And native potato starch (33.4 wt.%) Was prepared according to the procedure described in Example 1.

Nach Compoundierung der verschiedenen Rezepturvarianten wurden Blasfolien aus den hergestellten polymeren Materialien hergestellt und deren mechanische Eigenschaften bestimmt. Insbesondere wurden die Zugfestigkeit (ZF), Reißdehnung (RD) , MFR (MeIt Flow Rate) und Dart-Drop-Werte (Durchstoßfestigkeit) der Folien bestimmt .After compounding the various formulation variants, blown films were produced from the polymer materials produced and their mechanical properties were determined. In particular, the tensile strength (ZF), elongation at break (RD), MFR (MeIt Flow Rate) and dart drop values (puncture resistance) of the films.

Figur 1 zeigt die Zugfestigkeiten und Reißdehnungen der hergestellten Folien bei verschiedenen Stärkegehalten.Figure 1 shows the tensile strengths and elongation at break of the films produced at different levels of starch.

Im Vergleich zu einer aus der Vergleichsrezeptur hergestellten Standardfolie ohne Glycidyl-Additiv weist die entsprechende glycidyl-modifizierte Folie mit gleichem Stärkegehalt (33,4 Gew.%) eine wesentlich höhere Zugfestigkeit auf. Diese Differenz führt, auf Grund der mit zunehmendem Stärkeanteil allgemein abfallenden Zugwerte, zu vergleichbaren Zugfestigkeiten von Standardfolien mit 33,4 % Stärke und glycidyl- modifizierten Folien mit 40 % Stärke.In comparison with a standard film produced without a glycidyl additive from the comparative formulation, the corresponding glycidyl-modified film with the same starch content (33.4% by weight) has a substantially higher tensile strength. This difference leads to comparable tensile strengths of standard films with 33.4% strength and glycidyl-modified films with 40% strength due to the generally decreasing tensile strength with increasing starch content.

Gleichen Stärkegehalt vorausgesetzt, unterscheidet sich der Wert für die Reißdehnung der glycidyl-modifizierten Folie nicht von dem der Standardfolie. Durch den Einsatz von Glycidyl-Additiv kann jedoch selbst für eine Folie mit einem Stärkeanteil von 40 % das Niveau der Reißdehnung (= Elastizität) auf über 400 % gehalten werden.Assuming equal starch content, the elongation at break value of the glycidyl-modified film does not differ from that of the standard film. By using glycidyl additive, however, even for a film with a starch content of 40%, the level of elongation at break (= elasticity) can be kept above 400%.

Dabei ist zu berücksichtigen, dass Folien aus polyrαeren Material gleicher Zusammensetzung ohne Glycidyl-Additiv mit mehr als 34 % Stärkeanteil äußerst körnig, spröde und brüchig sind, so dass eine Ermittlung von mechanischen Kennwerten praktisch nicht möglich ist.It should be noted that films of polyrαeren material of the same composition without glycidyl additive with more than 34% starch content are extremely granular, brittle and brittle, so that a determination of mechanical characteristics is practically impossible.

In Figur 2 sind die MFR (MeIt Flow Rate) und die Dart- Drop-Werte (Durchstoßfestigkeit) von glycidyl- modifizierten Folien mit zunehmendem Stärkegehalt dargestellt . Aus Figur 2 geht hervor, dass mit zunehmendem Stärkegehalt beide Kurven nur leicht abfallen. Während die Dart-Drop-Werte für die Standardrezeptur ohne Glycidyl-Additiv und die modifizierte Rezeptur auf gleichem Niveau liegen, bewirkt das Glycidyl-Additiv eine MFR-Absenkung auf weniger als die Hälfte des Standardwertes .FIG. 2 shows the MFR (melt flow rate) and the dart drop (puncture resistance) of glycidyl-modified films with increasing starch content. From Figure 2 shows that with increasing starch content both curves fall only slightly. While the dart drop values for the standard formula without glycidyl additive and the modified formula are at the same level, the glycidyl additive causes an MFR reduction to less than half of the standard value.

Das im Vergleich zu der Standardfolie ohne Glycidyl- Additiv deutlich abgesenkte MFR-Niveau der glycidyl- behandelten Formulierungen ist - ohne auf eine bestimmte Theorie festgelegt zu sein - auf die epoxid-induzierte Vernetzung der Polymerketten zurückzuführen. Der MFR erscheint daher als geeigneter Parameter zur Beurteilung der chemischen Umsetzung entsprechender Kettenverlängerer/Vernetzer.The MFR level of the glycidyl-treated formulations, which is significantly reduced in comparison to the standard film without glycidyl additive, can be attributed to the epoxide-induced crosslinking of the polymer chains-without being bound to any particular theory. The MFR therefore appears to be a suitable parameter for assessing the chemical conversion of corresponding chain extenders / crosslinkers.

Beachtlich in Figur 2 sind auch die über den gesamten Bereich der Stärkeanreicherung stabilen Dart-Drop-Werte. Es bestätigt sich die bereits durch Auftragung von Zugfestigkeit und Reißdehnung (Figur 1) gemachte Beobachtung, dass durch Zugabe reaktiver Glycidyl- Additive zur Basisrezeptur einer üblicherweise mit steigendem Stärkeanteil zunehmenden Materialversprödung wirksam begegnet werden kann.Noteworthy in Figure 2 are also over the entire range of starch accumulation stable dart drop values. The observation already made by the application of tensile strength and elongation at break (FIG. 1) confirms that the addition of reactive glycidyl additives to the base formulation of a material embrittlement, which usually increases with increasing starch content, can be effectively counteracted.

Beispiel 3Example 3

In diesem Beispiel wurde der Einfluss unterschiedlicher Glycidyl-Additive auf die mechanischen Eigenschaften von stärkehaltigen Blasfolien bestimmt. _ 1 C _In this example, the influence of different glycidyl additives on the mechanical properties of starch-containing blown films was determined. _ 1 C _

Beispiel 2 wurde mit drei unterschiedlichen epoxidgruppenhaltigen Polymeren (Glycidyl-Additive) wiederholt .Example 2 was repeated with three different epoxy group-containing polymers (glycidyl additives).

Es wurden verschiedene stärkehaltige polymere Materialien aus aliphatisch-aromatischem Copolyester (59,5 bis 66,1 Gew.%), nativer Kartoffelstärke (33,4 bis 40 Gew.%) und epoxidgruppenhaltigem Copolymer (Additiv A, B oder C, siehe unten) (0,5 Gew.%) gemäß der in Beispiel 1 beschriebenen Vorgehensweise hergestellt. Der Mengenanteil der nativen Kartoffelstärke wurde dabei auf Kosten des aromatisch-aliphatischen Copolyesters zwischen 33,4 bis 40 Gew.% schrittweise variiert (siehe Figuren 3 und 4 ) .Various starchy polymeric materials have been prepared from aliphatic-aromatic copolyester (59.5 to 66.1 weight percent), native potato starch (33.4 to 40 weight percent), and epoxy group-containing copolymer (additive A, B or C, see below). (0.5 wt.%) Prepared according to the procedure described in Example 1. The proportion of native potato starch was varied stepwise from 33.4 to 40% by weight at the expense of the aromatic-aliphatic copolyester (see FIGS. 3 and 4).

Als Vergleichsrezeptur wurde polymeres Material ohne Glycidyl-Additiv aus aliphatisch-aromatischem Copolyester (66,6 Gew.%) und nativer Kartoffelstärke (33,4 Gew.%) gemäß der in Beispiel 1 beschriebenen Vorgehensweise hergestellt .As a comparative formulation, polymeric material without glycidyl additive of aliphatic-aromatic copolyester (66.6 wt.%) And native potato starch (33.4 wt.%) Was prepared according to the procedure described in Example 1.

Als Additiv A wurde ein statistisches Copolymer auf Basis von Styrol-Methylmethacrylat-Glycidylmethacrylat mit einem Molekulargewicht Mw von etwa 6800 und einem Epoxygruppenäquivalentgewicht von 285 g/mol eingesetzt.As additive A, a random copolymer based on styrene-methyl methacrylate-glycidyl methacrylate having a molecular weight M w of about 6800 and an epoxy group equivalent weight of 285 g / mol was used.

Als Additiv B wurde ein statistisches Copolymer auf Basis von Ethylen-Methylacrylat-Glycidylmethacrylat mit ca. 24 Gew.% Methylacrylat, 68 Gew.% Ethylen und 8 Gew.% Glycidylmethacrylat und einem Epoxygruppenäquivalentgewicht von 1775 g/mol eingesetzt. Als Additiv C wurde ein statistisches Copolymer auf Basis von Ethylen-Glycidylmethacrylat mit ca. 92 Gew.% Ethylen und 8 Gew.% Glycidylmethacrylat und einem Epoxygruppenäquivalentgewicht von 1775 g/mol eingesetzt.As additive B, a random copolymer based on ethylene-methyl acrylate-glycidyl methacrylate with about 24% by weight of methyl acrylate, 68% by weight of ethylene and 8% by weight of glycidyl methacrylate and an epoxy group equivalent weight of 1775 g / mol was used. As additive C, a random copolymer based on ethylene-glycidyl methacrylate with about 92% by weight of ethylene and 8% by weight of glycidyl methacrylate and an epoxy group equivalent weight of 1775 g / mol was used.

Die eingesetzten Glycidyl-Ädditive unterschieden sich insbesondere in ihrem Gehalt an reaktiven Epoxy- Einheiten. Die massebezogene Konzentration an Epoxy- Einheiten ist in Additiv A um den Faktor 6,23 höher als in den Additiven 2 und 3. Demnach enthalten, bei gleicher Einwaage, Additiv B resp. Additiv C weniger als ein Sechstel an reaktiven Epoxidgruppen im Vergleich zu Additiv A.The glycidyl-types used differed in particular in their content of reactive epoxy units. The mass-based concentration of epoxy units in additive A is higher by a factor of 6.23 than in additives 2 and 3. Accordingly, with the same initial weight, additive B resp. Additive C less than one-sixth of reactive epoxide groups compared to Additive A.

Diese signifikante Differenz wirkt sich entsprechend deutlich auf die Eigenschaften vergleichbar hergestellter Rezepturen aus.This significant difference has a correspondingly significant effect on the properties of comparably prepared formulations.

Die Figuren 3 und 4 zeigen exemplarisch die stärkegehaltabhängige Entwicklung von Zugfestigkeit und MFR von stärkehaltigen polymeren Materialien gemäß Beispiel 2, versetzt mit jeweils 0,5 % der Additive A, B oder C.FIGS. 3 and 4 show, by way of example, the starch content-dependent development of tensile strength and MFR of starch-containing polymeric materials according to Example 2, mixed with in each case 0.5% of the additives A, B or C.

Aus Figur 3 geht hervor, dass die Zugfestigkeit der Folien bei Additiv A mit zunehmendem Stärkegehalt linear ansteigt, während sie bei den Additiven 2 und 3 abnimmt.FIG. 3 shows that the tensile strength of the films in the case of additive A increases linearly with increasing starch content, whereas it decreases in the case of additives 2 and 3.

Aus Figur 4 geht hervor, dass die allesamt mit steigendem Stärkeanteil linear leicht abfallenden MFR-Werte für das mit Additiv A behandelte Material auf sehr niedrigem Niveau liegen. Ein Vergleich der mit den Additiven 2 bzw. 3 behandelten Materialien mit einer Standardfolie ohne Glycidyl-Additiv lässt dagegen keinen nennenswerten Einfluss des Glycidyl-Additivs auf die MeIt Flow Rate erkennen .FIG. 4 shows that the MFR values, which decrease linearly with increasing starch content, are very low for the material treated with additive A. A comparison of the treated with the additives 2 and 3 materials with a standard film without Glycidyl additive, on the other hand, does not reveal any appreciable influence of the glycidyl additive on the MeIt flow rate.

Die in den Figuren 3 und 4 dargestellten Kurvenverläufe zeigen, dass ein merklicher Einfluss der Additive 2 und 3 auf die mechanischen Eigenschaften der Folien bei der verwendeten Konzentration von 0,5 Gew.% kaum feststellbar ist. Gleichwohl wurde auch bei den Additiven B und C in der verwendeten Konzentration eine Verbesserung der Kompatibilität der Bestandteile Stärke und Polyester gegenüber der Vergleichsrezeptur ohne Glycidyl-Additiv festgestellt .The curves shown in FIGS. 3 and 4 show that a noticeable influence of the additives 2 and 3 on the mechanical properties of the films at the concentration of 0.5% by weight used is barely detectable. Nevertheless, an improvement in the compatibility of the ingredients starch and polyester compared to the comparison formulation without glycidyl additive was also found in the additives used in additives B and C.

Beispiel 4Example 4

In diesem Beispiel wurde der Einfluss unterschiedlicher Konzentrationen von epoxidgruppenhaltigem Polymer (Glycidyl-Additiv) auf die mechanischen Eigenschaften von Blasfolien mit einem Stärkegehalt von bis zu 42 Gew.% bestimmt .In this example, the influence of different concentrations of epoxy group-containing polymer (glycidyl additive) on the mechanical properties of blown films having a starch content of up to 42 wt.% Was determined.

Auf einer Produktionsanlage (ZSK 70/7) wurde zunächst die Wirksamkeit unterschiedlicher Additivkonzentrationen überprüft. Hierzu wurden Materialien mit drei verschiedenen Additivkonzentrationen compoundiert (0,1 Gew.% Glycidyl-Ädditiv, 0,5 Gew.% Glycidyl-Additiv und eine Vergleichsrezeptur (Standard) ohne Additiv) . Als epoxidgruppenhaltiges Polymer wurde Additiv A aus Beispiel 3 verwendet. Es wurden verschiedene stärkehaltige polymere Materialien aus aliphatisch-aromatischem Copolyester (57,5 bis 66,5 Gew.%), nativer Kartoffelstärke (33,4 bis 42 Gew.%) und epoxidgruppenhaltiges Polymer (0,1 bzw. 0,5 Gew.%) gemäß Beispiel 1 hergestellt. Der Mengenanteil der nativen Kartoffelstärke wurde dabei auf Kosten des aromatisch- aliphatischen Copolyesters zwischen 33,4 bis 42 Gew.% schrittweise variiert (siehe Figuren 5 und 6) . Ebenso wurde der Mengenanteil des epoxidgruppenhaltigen Polymers (Additiv A) auf Kosten des aromatisch-aliphatischen Copolyesters variiert.On a production plant (ZSK 70/7), the effectiveness of different additive concentrations was first examined. For this purpose, materials with three different additive concentrations were compounded (0.1% by weight of glycidylidene, 0.5% by weight of glycidyl additive and a comparison formulation (standard) without additive). The epoxy-containing polymer used was additive A from example 3. Various starchy polymeric materials of aliphatic-aromatic copolyester (57.5 to 66.5 wt.%), Native potato starch (33.4 to 42 wt.%) And epoxy group-containing polymer (0.1 and 0.5 wt. %) prepared according to Example 1. The proportion of native potato starch was varied stepwise from 33.4 to 42% by weight at the expense of the aromatic-aliphatic copolyester (see FIGS. 5 and 6). Likewise, the proportion of the epoxide group-containing polymer (additive A) was varied at the expense of the aromatic-aliphatic copolyester.

Als Vergleichsrezeptur wurde polymeres Material ohne Glycidyl-Additiv aus aliphatisch-aromatischem Copolyester (66,6 Gew.%) und nativer Kartoffelstärke (33,4 Gew.%) gemäß der in Beispiel 1 beschriebenen Vorgehensweise hergestellt .As a comparative formulation, polymeric material without glycidyl additive of aliphatic-aromatic copolyester (66.6 wt.%) And native potato starch (33.4 wt.%) Was prepared according to the procedure described in Example 1.

Figur 5 zeigt den Verlauf der MeIt Flow Rate (MFR) von aus den Materialien hergestellten Blasfolien in Abhängigkeit des Stärkegehaltes und der Additiv- Konzentration. Aus den Werten ist ersichtlich, dass sich die MeIt Flow Rate (MFR) (d. h. die Fließfähigkeit) mit steigendem Stärkegehalt und zunehmender Glycidyl- Konzentration in den Materialien reduziert . Im Vergleich zur Standardrezeptur (Kreis) sinkt der MFR-Wert der Formulierung mit 42 Gew.% Stärke und 0,5 Gew.% Glycidyl- Additiv auf weniger als ein Fünftel ab (Dreieck), ein Zeichen für umfangreiche Vernetzung der enthaltenen Polymere .FIG. 5 shows the profile of the melt flow rate (MFR) of blown films produced from the materials as a function of the starch content and the additive concentration. From the data, it can be seen that the melt flow rate (MFR) (i.e., fluidity) decreases with increasing starch content and increasing glycidyl concentration in the materials. Compared to the standard formula (circle), the MFR value of the formulation with 42% by weight starch and 0.5% by weight glycidyl additive drops to less than one fifth (triangle), a sign of extensive crosslinking of the polymers contained.

Ohne auf eine bestimmte Theorie festgelegt zu sein, kann dieser Verlauf mit einer Vernetzungsreaktion des Glycidyl-Additivs mit dem Polyester bzw. der Stärke erklärt werden. Die sprunghafte MFR-Halbierung bei 40 Gew.% Stärke im Übergang von durchgezogener zu gestrichelter Kurve zeigt, dass der absinkende MFR-Wert nicht allein auf eine Erhöhung des Stärkeanteils (wie dies im Falle der durchgezogenen Kurve zwischen 33 und 40 Gew.% der Fall ist), sondern maßgeblich auch auf eine vermehrte Umsetzung des konzentrierter eingesetzten Glycidyl-Additivs zurückgeführt werden kann.Without being bound to a particular theory, this course may be followed by a crosslinking reaction of the Glycidyl additive can be explained with the polyester or the starch. The erratic MFR halving at 40% by weight of the solid-to-dashed curve transition shows that the decreasing MFR value is not due solely to an increase in starch content (as in the case of the solid curve, between 33 and 40% by weight) is), but can be significantly attributed to an increased implementation of the concentrated glycidyl additive used.

In Figur 6 ist der Verlauf von Zugfestigkeit (ZF), Reißdehnung (RD) und Dart Drop (DD) für Folien mit unterschiedlichen Gehalten an Stärke und Glycidyl-Additiv dargestellt. Während ZF und RD mit steigendem Stärkegehalt abnehmen, verbleibt der DD-Wert auf konstantem Niveau.FIG. 6 shows the profile of tensile strength (ZF), elongation at break (RD) and dart drop (DD) for films with different levels of starch and glycidyl additive. While ZF and RD decrease with increasing starch content, the DD value remains at a constant level.

Aus Figur 6 ist ersichtlich, dass die mit steigendem Stärkeanteil linear abnehmende Reißdehnung durch Zugabe von Glycidyl-Additiv nicht merklich beeinflusst wird. Selbst bei 0,5 Gew.% Additivanteil (durchgezogene Kurve) sinkt der Wert nach Überschreiten von 40 Gew.% Stärke weiter ab. Die Durchstoßfestigkeit (DD-Wert) hält sich über den gesamten untersuchten Bereich auf konstantem Niveau .It can be seen from FIG. 6 that the linearly decreasing elongation at break with increasing starch content is not noticeably influenced by the addition of glycidyl additive. Even with 0.5% by weight of additive (solid curve), the value continues to fall after exceeding 40% by weight of starch. The puncture resistance (DD value) remains at a constant level over the entire investigated area.

Ohne auf eine bestimmte Theorie festgelegt zu sein, wird angenommen, dass der Effekt eines mit steigendem Stärkeanteil üblicherweise abnehmenden DD-Wertes (d. h. Folie wird spröder) durch die Polymervernetzung mit dem Glycidyl-Additiv kompensiert wird. Die bei höherem Glycidyl-Additiv-Gehalt umfangreichere Strangverknüpfung lässt sich durch eine signifikant höhere Zugfestigkeit bei gleichem Stärkeanteil nachweisen (sprunghafter Übergang der strichpunktierten Kurve bei 40 Gew.% Stärke) .Without wishing to be bound by any particular theory, it is believed that the effect of a normally decreasing DD value (ie, film becomes more brittle) as the starch level increases is compensated for by polymer crosslinking with the glycidyl additive. The higher strand linkage at higher glycidyl additive content can be significantly enhanced Higher tensile strength with the same amount of starch prove (abrupt transition of the dash-dotted curve at 40 wt.% strength).

Beispiel 5Example 5

In diesem Beispiel wurden die Glycidyl-Additive 1 und 2 aus Beispiel 3 bei äquivalenten Glycidyl-Anteilen verglichen .In this example, the glycidyl additives 1 and 2 of Example 3 were compared at equivalent glycidyl levels.

Zunächst wurde ein stärkehaltiges polymeres Material aus aliphatisch-aromatischem Copolyester (59,9 Gew.%), nativer Kartoffelstärke (40 Gew.%) und Additiv A aus Beispiel 3 (0,1 Gew.%) gemäß der in Beispiel 1 beschriebenen Vorgehensweise hergestellt.First, a starchy polymeric material was prepared from aliphatic-aromatic copolyester (59.9 wt.%), Native potato starch (40 wt.%) And additive A from Example 3 (0.1 wt.%) According to the procedure described in Example 1 ,

Anschließend wurde ein stärkehaltiges polymeres Material aus aliphatisch-aromatischem Copolyester (59,4 Gew.%), nativer Kartoffelstärke (40 Gew.%) und Additiv B aus Beispiel 3 (0,6 Gew.%) gemäß der in Beispiel 1 beschriebenen Vorgehensweise hergestellt.Subsequently, a starchy polymeric material of aliphatic-aromatic copolyester (59.4 wt.%), Native potato starch (40 wt.%) And additive B of Example 3 (0.6 wt.%) Was prepared according to the procedure described in Example 1 ,

Die beiden so hergestellten Materialien bzw. daraus hergestellte Blasfolien wurden miteinander verglichen. Figur 7 zeigt die Resultate:The two materials thus produced or blown films produced therefrom were compared with one another. FIG. 7 shows the results:

Figur 7 zeigt, dass die Additive 1 und 2 bei mengenmäßig äguivalenten Glycidyl-Anteilen (0,1 Gew.% Additiv A versus 0,6 Gew.% Additiv B) zu vergleichbaren Materialeigenschaften des polymeren Materials führen. Einzig der Wert für die Reißdehnung (RD) ist bei der Additiv B enthaltenden Folie merklich höher. Im Ergebnis lässt sich anhand der durchgeführten Versuche Folgendes feststellen :FIG. 7 shows that additives 1 and 2 lead to comparable material properties of the polymeric material with quantitatively equivalent glycidyl fractions (0.1% by weight of additive A versus 0.6% by weight of additive B). Only the value for the elongation at break (RD) is markedly higher in the case of the additive B-containing film. As a result, based on the experiments carried out, the following can be stated:

Die Materialeigenschaften gattungsgemäßer stärkehaltiger polymerer Materialien lassen sich durch Zugabe glycidyl- haltiger Additive signifikant verändern . Während herkömmliche stärkehaltige polymere Materialien ohne Glycidyl-Additiv oberhalb von etwa 34 Gew . % unzureichende mechanische Eigenschaften aufweisen, ermöglicht bereits ein Gehalt von 0 , 1 % von Glycidyl-Additiv die Herstellung eines polymeren Materials mit einem Stärkegehalt von 40 Gew . % bei gleichzeitig ausgezeichneten mechanischen Eigenschaften .The material properties of generic starch-containing polymeric materials can be significantly changed by adding glycidyl-containing additives. While conventional starchy polymeric materials lack glycidyl additive above about 34 wt. % have insufficient mechanical properties, already allows a content of 0.1% of glycidyl additive, the production of a polymeric material having a starch content of 40 wt. % with simultaneously excellent mechanical properties.

Während die Erhöhung des Stärkeanteils zwangsläufig zu Lasten der Elastizität des glycidyl-modif izierten Material s geht , wird die Durchstoßfestigkeit des glycidyl-modif i zierten Materials durch eine Erhöhung des Stärkeanteils nicht beeinflusst .While the increase in the starch content is inevitably at the expense of the elasticity of the glycidyl-modified material s, the puncture resistance of the glycidyl-modified material is not affected by an increase in the starch content.

Ohne sich auf eine bestimmte Theorie festzulegen, wird angenommen , dass das Glycidyl-Additiv als Compatibilizer zwischen den ansonsten unverträglichen Polymeren Stärke und Polyester wirkt . Die Ef fizienz der Polymervernetzung manifestiert sich in erhöhten Zugfestigkeitswerten bei gleichzeitig niedriger Schmelzflussrate (MFR) .Without wishing to be bound by theory, it is believed that the glycidyl additive acts as a compatibilizer between the otherwise incompatible polymers starch and polyester. The efficiency of polymer crosslinking manifests itself in increased tensile strength values while maintaining a low melt flow rate (MFR).

Die Erfindung ist vorstehend anhand von Ausführungsbeispielen exemplarisch bes chrieben worden . Dabei versteht sich, dass die Erfindung nicht auf die beschriebenen Ausführungsbeispiele beschränkt ist . Vielmehr ergeben sich für den Fachmann im Rahmen der Erfindung vielfältige Abwandlungs- und Modifikationsmöglichkeiten und der Schutzumfang der Erfindung wird insbesondere durch die nachfolgenden Patentansprüche festgelegt. The invention has been described above by way of examples by way of example. It is understood that the invention is not limited to the described embodiments. Rather, arise for the expert in the context of Invention diverse modification and modification options and the scope of the invention is set forth in particular by the following claims.

Claims

Patentansprüche claims 1. Verfahren zur Hersteilung eines stärkehaltigen polymeren Materials, gekennzeichnet durch:A process for the preparation of a starchy polymeric material characterized by: (a) Herstellen eines Gemischs enthaltend wenigstens(a) preparing a mixture containing at least - 1 bis 75 Gew.% Stärke und/oder Stärkederivat,From 1 to 75% by weight of starch and / or starch derivative, - 10 bis 85 Gew.% Polyester und10 to 85% by weight of polyester and - 0,01 bis 7 Gew.% eines epoxidgruppenhaltigen Polymers;0.01 to 7% by weight of an epoxy group-containing polymer; (b) Homogenisieren des Gemischs unter Zuführen von thermischer und/oder mechanischer Energie;(b) homogenizing the mixture by applying thermal and / or mechanical energy; (c) Einstellen des Wassergehalts des Gemischs, so dass das Endprodukt einen Wassergehalt von kleiner etwa 12 Gew.%, bezogen auf die Gesamtzusammensetzung des Gemischs, aufweist.(c) adjusting the water content of the mixture so that the final product has a water content of less than about 12% by weight, based on the total composition of the mixture. 2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass das Gemisch 5 bis 75 Gew.%, insbesondere 10 bis 75 Gew.%, vorzugsweise 15 bis 70 Gew.%, noch bevorzugter 25 bis 55 Gew.%, am bevorzugtesten 34 bis 51 Gew.% Stärke und/oder Stärkederivat enthält. 2. The method according to claim 1, characterized in that the mixture 5 to 75 wt.%, In particular 10 to 75 wt.%, Preferably 15 to 70 wt.%, More preferably 25 to 55 wt.%, Most preferably 34 to 51 % By weight of starch and / or starch derivative. 3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass das Gemisch 20 bis 85 Gew.%, insbesondere 30 bis 80 Gew.%, noch bevorzugter 40 bis 80 Gew.% Polyester enthält.3. The method according to claim 1 or 2, characterized in that the mixture 20 to 85 wt.%, In particular 30 to 80 wt.%, More preferably 40 to 80 wt.% Polyester contains. 4. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass das Gemisch 0,01 bis 5 Gew.%, insbesondere 0,05 bis 3 Gew.%, noch bevorzugter 0,1 bis 2 Gew.% epoxidgruppenhaltiges Polymer enthält.4. The method according to any one of the preceding claims, characterized in that the mixture contains 0.01 to 5 wt.%, In particular 0.05 to 3 wt.%, More preferably 0.1 to 2 wt.% Epoxide group-containing polymer. 5. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass das polymere Material gemäß EN 13432 biologisch abbaubar ist.5. The method according to any one of the preceding claims, characterized in that the polymeric material according to EN 13432 is biodegradable. 6. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass der Polyester ausgewählt ist aus der Gruppe bestehend aus aliphatisch-aromatischem Copolyester, aliphatischem Polyester, aromatischen Polyester, PHA, PLA, PHB und PHBV.6. The method according to any one of the preceding claims, characterized in that the polyester is selected from the group consisting of aliphatic-aromatic copolyester, aliphatic polyester, aromatic polyester, PHA, PLA, PHB and PHBV. 7. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass der Polyester eine Glasübergangstemperatur (Tg) kleiner 00C, insbesondere kleiner -40C, weiter bevorzugt kleiner -1O0C, noch weiter bevorzugt kleiner -2O0C und am bevorzugtesten kleiner -3O0C aufweist.7. The method according to any one of the preceding claims, characterized in that the polyester has a glass transition temperature (Tg) less than 0 0 C, especially less -4 0 C, more preferably less than -1O 0 C, even more preferably less than -2O 0 C and most preferably less than -3O 0 C. 8. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass als aliphatisch-aromatischer Polyester ein Copolyester, insbesondere ein statistischer Copolyester, auf Basis von mindestens Adipinsaure eingesetzt wird. 8. The method according to any one of the preceding claims, characterized in that is used as the aliphatic-aromatic polyester, a copolyester, in particular a random copolyester, based on at least adipic acid. 9. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass als aliphatisch-aromatischer Polyester ein Copolyester, insbesondere ein statistischer Copolyester, auf Basis von 1, 4-Butandiol, Adipinsäure und Terephthalsäure bzw. Terephthalsäurederivat (z. B. Dimethylterephthalat DMT) eingesetzt wird.9. The method according to any one of the preceding claims, characterized in that as aliphatic-aromatic polyester, a copolyester, in particular a random copolyester, based on 1, 4-butanediol, adipic acid and terephthalic acid or terephthalic acid derivative (eg., Dimethylterephthalat DMT) becomes. 10. Verfahren nach Anspruch 10, dadurch gekennzeichnet, dass der Polyester eine Glasübergangstemperatur (Tg) von -25 bis -400C, insbesondere -30 bis -350C, und/oder einen Schmelzbereich von 100 bis 12O0C, insbesondere 105 bis 1150C, aufweist.10. The method according to claim 10, characterized in that the polyester has a glass transition temperature (Tg) of -25 to -40 0 C, in particular -30 to -35 0 C, and / or a melting range of 100 to 12O 0 C, in particular 105 to 115 0 C, has. 11. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass der Polyester ein aliphatischer Polyester ausgewählt aus der Gruppe bestehend aus Polyhydroxvalerat, Polyhydroxybutyrat- Hydroxyvalerat-Copolymer und Polycaprolacton ist.11. The method according to any one of the preceding claims, characterized in that the polyester is an aliphatic polyester selected from the group consisting of polyhydroxvalerate, polyhydroxybutyrate hydroxyvalerate copolymer and polycaprolactone. 12. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass der Polyester ein aliphatischer Polyester auf Succinat-Basis ist, wobei der Polyester insbesondere ausgewählt ist aus der Gruppe bestehend aus Polybutylensuccinat (PBS),12. The method according to any one of the preceding claims, characterized in that the polyester is a succinate-based aliphatic polyester, wherein the polyester is in particular selected from the group consisting of polybutylene succinate (PBS), Polybutylensuccinatadipat (PBSA) und Polyethylensuccinat (PES) .Polybutylene succinate adipate (PBSA) and polyethylene succinate (PES). 13. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass der Polyester gemäß EN 13432 biologisch abbaubar ist. 13. The method according to any one of the preceding claims, characterized in that the polyester is biodegradable according to EN 13432. 14. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass das epoxidgruppenhaltige Polymer ein Copolymer ist.14. The method according to any one of the preceding claims, characterized in that the epoxide group-containing polymer is a copolymer. 15. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass das epoxidgruppenhaltige Polymer ein glycidyl (meth) acrylathaltiges Polymer ist.15. The method according to any one of the preceding claims, characterized in that the epoxy group-containing polymer is a glycidyl (meth) acrylate-containing polymer. 16. Verfahren nach Anspruch 15, dadurch gekennzeichnet, dass das glycidyl (meth) acrylathaltige Polymer ein Copolymer aus (a) Styrol und/oder Ethylen und/oder Methylmethacrylat und/oder Methylacrylat und (b) Glycidyl (meth) acrylat ist.16. The method according to claim 15, characterized in that the glycidyl (meth) acrylate-containing polymer is a copolymer of (a) styrene and / or ethylene and / or methyl methacrylate and / or methyl acrylate and (b) glycidyl (meth) acrylate. 17. Verfahren nach Anspruch 15 oder 16, dadurch gekennzeichnet, dass das glycidyl (meth) acrylathaltige Polymer ein epoxidgruppenhaltiges Copolymer auf Basis von Styrol, Ethylen, Acrylsäureester und/oder Methacrylsäureester ist.17. The method according to claim 15 or 16, characterized in that the glycidyl (meth) acrylate-containing polymer is an epoxide group-containing copolymer based on styrene, ethylene, acrylic acid ester and / or methacrylic acid ester. 18. Verfahren nach einem der Ansprüche 15 bis 17, dadurch gekennzeichnet, dass das glycidyl (meth) acrylathaltige Polymer ein Copolymer ist, welches ausgewählt ist aus der Gruppe bestehend aus Styrol-Methylmethacrylat- Glycidylmethacrylat, Ethylen-Methylacrylat- Glycidylmethacrylat und Ethylen-Glycidylmethacrylat .18. The method according to any one of claims 15 to 17, characterized in that the glycidyl (meth) acrylate-containing polymer is a copolymer which is selected from the group consisting of styrene-methyl methacrylate-glycidyl methacrylate, ethylene-methyl acrylate-glycidyl methacrylate and ethylene-glycidyl methacrylate. 19. Verfahren nach einem der Ansprüche 15 bis 18, dadurch gekennzeichnet, dass das glycidyl (meth) acrylathaltige Polymer19. The method according to any one of claims 15 to 18, characterized in that the glycidyl (meth) acrylate-containing polymer Glycidyl (meth) acrylat in einer Menge von 1 bis 60 Gew.%, insbesondere 5 bis 55 Gew.%, weiter bevorzugt 45 bis 52 Gew.%, bezogen auf die Gesamtzusammensetzung des glycidyl (meth) acrylathaltigen Polymers, enthält.Glycidyl (meth) acrylate in an amount of 1 to 60 wt.%, In particular 5 to 55 wt.%, More preferably 45 to 52nd % By weight, based on the total composition of the glycidyl (meth) acrylate-containing polymer. 20. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass das epoxidgruppenhaltige Polymer ein Molekulargewicht (Mw) von 1.000 bis 25.000 insbesondere 3.000 bis 10.000 aufweist.20. The method according to any one of the preceding claims, characterized in that the epoxy group-containing polymer has a molecular weight (M w ) of 1,000 to 25,000, in particular 3,000 to 10,000. 21. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass das Homogenisieren des Gemischs durch Dispergieren, Rühren, Kneten und/oder Extrudieren erfolgt.21. The method according to any one of the preceding claims, characterized in that the homogenization of the mixture by dispersing, stirring, kneading and / or extrusion takes place. 22. Verfahren nach Anspruch 21, dadurch gekennzeichnet, dass das Homogenisieren des Gemischs durch Extrusion erfolgt .22. The method according to claim 21, characterized in that the homogenization of the mixture is carried out by extrusion. 23. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass das Homogenisieren des Gemischs durch Einwirken von Scherkräften auf das Gemisch erfolgt .23. The method according to any one of the preceding claims, characterized in that the homogenization of the mixture takes place by the action of shear forces on the mixture. 24. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass das Gemisch beim Homogenisieren bzw. Extrudieren auf eine Temperatur von 90 bis 25O0C, insbesondere 130 bis 22O0C, erwärmt wird.24. The method according to any one of the preceding claims, characterized in that the mixture during homogenization or extrusion to a temperature of 90 to 25O 0 C, in particular 130 to 22O 0 C, is heated. 25. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass der Wassergehalt des Gemischs auf kleiner 10 Gew.%, insbesondere kleiner 7 Gew.%, weiter bevorzugt kleiner 5 Gew.%, insbesondere kleiner 3 Gew.%, noch bevorzugter kleiner 1,5 Gew.% und am bevorzugtesten kleiner 1 Gew . % , bezogen auf die Gesamtzusammensetzung, eingestellt wird.25. The method according to any one of the preceding claims, characterized in that the water content of the mixture to less than 10 wt.%, In particular less than 7 wt.%, More preferably less than 5 wt.%, In particular less than 3 wt.%, More preferably less than 1 , 5% by weight and most preferably less than 1 wt. %, based on the total composition. 26. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass der Wassergehalt des Gemischs während des Homogenisierens eingestellt wird.26. The method according to any one of the preceding claims, characterized in that the water content of the mixture is adjusted during homogenization. 27. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass der Wassergehalt des Gemischs durch Entgasen des Gemischs, insbesondere durch Entgasen der Schmelze, eingestellt wird.27. The method according to any one of the preceding claims, characterized in that the water content of the mixture by degassing of the mixture, in particular by degassing of the melt is adjusted. 28. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass der Wassergehalt des Gemischs durch Trocknen des Gemischs während des Homogenisierens bzw. Extrudierens eingestellt wird.28. The method according to any one of the preceding claims, characterized in that the water content of the mixture is adjusted by drying the mixture during the homogenization or extrusion. 29. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass eine aus dem polyrneren Material hergestellte Folie eine Zugfestigkeit gemäß DIN 53455 von 5 bis 60 N/mm2, insbesondere von 10 bis 40 N/mm2 aufweist .29. The method according to any one of the preceding claims, characterized in that a film made of the polyrneren material has a tensile strength according to DIN 53455 of 5 to 60 N / mm 2 , in particular from 10 to 40 N / mm 2 . 30. Verfahren nach einem der vorstehenden Ansprüche, dadurch gekennzeichnet, dass eine aus dem polymeren Material hergestellte Folie eine Reißdehnung gemäß DIN 53455 von 100 bis 1000 %, insbesondere von 200 bis 800 %, aufweist .30. The method according to any one of the preceding claims, characterized in that a film produced from the polymeric material has an elongation at break according to DIN 53455 of 100 to 1000%, in particular from 200 to 800%. 31. Polymeres Material hergestellt nach einem Verfahren gemäß einem der Ansprüche 1 bis 30. 31. A polymeric material prepared by a process according to any one of claims 1 to 30. 32. Stärkehaltiges thermoplastisch verarbeitbares polymeres Material, dadurch gekennzeichnet, dass32. starch-containing thermoplastically processable polymeric material, characterized in that (a) das polymere Material weniger als 10 Gew.%, bezogen auf die Gesamtzusammensetzung, niedermolekulare Substanzen enthält,(a) the polymeric material contains less than 10% by weight, based on the total composition, of low molecular weight substances, (b) der Stärkeanteil des polymeren Materials mindestens 34 Gew.% beträgt und(b) the amount of starch of the polymeric material is at least 34% by weight, and (c) eine aus dem polymeren Material hergestellte Folie eine Reißdehnung gemäß DIN 53455 von mindestens 200 % und/oder einen Dart-Drop-Wert gemäß ASTM D-1709 von mindestens 5 g/μm aufweist.(c) a film produced from the polymeric material has an elongation at break according to DIN 53455 of at least 200% and / or a dart drop value according to ASTM D-1709 of at least 5 g / μm. 33. Polymeres Material nach Anspruch 32, dadurch gekennzeichnet, dass niedermolekulare Substanzen mit einem Molekulargewicht kleiner 500 g/mol, insbesondere kleiner 250 g/mol, sind.33. Polymeric material according to claim 32, characterized in that low molecular weight substances having a molecular weight of less than 500 g / mol, in particular less than 250 g / mol. 34. Polymeres Material nach Anspruch 32 oder 33, dadurch gekennzeichnet, dass die niedermolekularen Substanzen Wasser, Glycerin, Sorbitol und/oder Mischungen daraus umfassen .34. Polymeric material according to claim 32 or 33, characterized in that the low molecular weight substances include water, glycerol, sorbitol and / or mixtures thereof. 35. Polymeres Material nach einem der Ansprüche 32 bis35. A polymeric material according to any one of claims 32 to 34, dadurch gekennzeichnet, dass das polymere Material weniger als 7 Gew.%, insbesondere weniger als 5 Gew.%, vorzugsweise weniger als 3 Gew.%, bezogen auf die Gesamtzusammensetzung, niedermolekulare Substanzen enthält .34, characterized in that the polymeric material less than 7 wt.%, In particular less than 5 wt.%, Preferably less than 3 wt.%, Based on the total composition, low molecular weight substances. 36. Polymeres Material nach einem der Ansprüche 32 bis36. A polymeric material according to any one of claims 32 to 35, dadurch gekennzeichnet, dass der Stärkeanteil des polymeren Materials mindestens 35 Gew.%, insbesondere mindestens 36 Gew.%, vorzugsweise mindestens 37 Gew.%, weiter bevorzugt mindestens 38 Gew.% und am bevorzugtesten mindestens 39 Gew.% beträgt.35, characterized in that the starch content of the polymeric material at least 35 wt.%, In particular at least 36 wt.%, Preferably at least 37 wt.%, more preferably at least 38% by weight, and most preferably at least 39% by weight. 37. Polymeres Material nach einem der Ansprüche 32 bis37. A polymeric material according to any one of claims 32 to 36, dadurch gekennzeichnet, dass eine aus dem polymeren Material hergestellte Folie eine Reißdehnung gemäß DIN 53455 von mindestens 300 % und/oder einen Dart-Drop-Wert gemäß ASTM D-1709 von mindestens 10 g/μm aufweist.36, characterized in that a film produced from the polymeric material has an elongation at break according to DIN 53455 of at least 300% and / or a dart drop value according to ASTM D-1709 of at least 10 g / μm. 38. Polymeres Material nach einem der Ansprüche 32 bis38. A polymeric material according to any one of claims 32 to 37, dadurch gekennzeichnet, dass das polymere Material als weiteren Bestandteil einen Polyester, vorzugsweise in einer Menge kleiner 70 Gew.%, insbesondere kleiner 65 Gew.%, noch bevorzugter kleiner 60 Gew.%, am bevorzugtesten kleiner 55 Gew.%, enthält.37, characterized in that the polymeric material contains as a further constituent a polyester, preferably in an amount less than 70 wt.%, In particular less than 65 wt.%, More preferably less than 60 wt.%, Most preferably less than 55 wt.%. 39. Polymeres Material nach einem der Ansprüche 32 bis39. A polymeric material according to any one of claims 32 to 38, dadurch gekennzeichnet, dass der Polyester ein Polyester gemäß einem der Ansprüche 6 bis 13 ist.38, characterized in that the polyester is a polyester according to any one of claims 6 to 13. 40. Verwendung eines polymeren Materials nach einem der vorstehenden Ansprüche zur Herstellung von Formteilen, Folien oder Fasern.40. Use of a polymeric material according to any one of the preceding claims for the production of moldings, films or fibers. 41. Formteile, Folien oder Fasern, enthaltend ein polymeres Material nach einem der Ansprüche 31 bis 39. 41. Moldings, films or fibers containing a polymeric material according to any one of claims 31 to 39.
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WO2009053383A1 (en) 2009-04-30
EP2203511B1 (en) 2012-02-29
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RS55435B2 (en) 2022-11-30
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PL2497797T3 (en) 2017-03-31
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